The recent development of the density matrix renormalization group (DMRG) method in multireference quantum chemistry makes it practical to evaluate static correlation in a large active space, while dynamic correlation provides a critical correction to the DMRG reference for strong-correlated systems and is usually obtained using multi-reference perturbation (MRPT) or configuration interaction (MRCI) methods with internal contraction (ic) approximation. These methods can use active space scalable to relatively larger size references than has previously been possible. However, they are still hardly applicable to systems with active space larger than 30 orbitals because of high computation and storage costs of high-order reduced density matrices (RDMs) and the number of virtual orbitals are normally limited to few hundreds. In this work, we propose a new effective implementation of DMRG-MRCI, in which we use re-constructed CASCI-type configurations from DMRG wave function via the entropy-driving genetic algorithm (EDGA), and integrate with MRCI by an external contraction (ec) scheme. This bypasses the bottleneck of computing high-order RDMs in traditional DMRG dynamic correlation methods with ic approximation and the number of MRCI configurations is not dependent on the number of virtual orbitals. Therefore, DMRG-ec-MRCI method is promising for dealing with larger active space than 30 orbitals and large basis sets. We demonstrate the capability of our DMRG-ec-MRCI method in several benchmark applications, including the evaluation of potential energy curve of Cr$_{2}$, single-triplet gaps of higher n-acene molecules and the energy of Eu-BTBP(NO$_3$)$_3$ complex.
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